CN103140559B - High-solid adhesive composition - Google Patents
High-solid adhesive composition Download PDFInfo
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- CN103140559B CN103140559B CN201280003191.6A CN201280003191A CN103140559B CN 103140559 B CN103140559 B CN 103140559B CN 201280003191 A CN201280003191 A CN 201280003191A CN 103140559 B CN103140559 B CN 103140559B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention addresses the problem of providing a two-pack curable adhesive composition for laminating which can be applied even when having a nonvolatile content of 50 mass% or higher and which has excellent laminating properties. The adhesive composition causes no problem of delamination, etc. when the laminate is subjected to high-temperature sterilization such as boiling or retortion. The two-pack curable adhesive composition for laminating comprises a polyester polyol ingredient as the main component and a polyisocyanate ingredient as a hardener, and is characterized in that the polyester polyol ingredient as the main component was obtained using a polycarboxylic acid or polycarboxylic acid anhydride that contained aromatic rings derived from the orthophthalic acid or phthalic anhydride (OPA) used as a starting material, in an amount of 2.0 mmol or more per g of the solid matter, and that the polyester polyol as the main component has a number-average molecular weight of 4,000 or lower.
Description
Technical field
The present invention relates to high solid type adhesive composite, in more detail, relate to the high solid type adhesive composite using in the used for packing foods caking agent that makes the laminatings such as plastic film, tinsel, paper, industrial caking agent etc.
Background technology
In order to give the designability of food product pack, industrial products etc., functional, storage characteristics, convenience, transportation etc., lamination is extensively universal in the laminating of the laminating materials such as diversified film, tinsel, paper with caking agent.
In recent years, around the environment of Flexible-Packaging Industry transmodulator, as topsoil, prevent that the discharge regulation of VOC of modification defined of method is, a ring of LCA (life cycle assessment) can be seen the CO bringing towards " visual " as carbon footprint
2the trend of the effort of minimizing direction etc.Therefore, lamination is also expected the goods that economize on resources conserve energy, can further reduce costs with caking agent.
The conserve energy that economizes on resources as lamination caking agent reduces costs strategy, and no-solvent type caking agent, high solid get most of the attention.Known have using polyhydroxy reactant as host, using polymeric polyisocyanate composition as the solvent-borne type two-solution curing type of solidifying agent adhesive composite (for example,, referring to patent documentation 1) for lamination.Usually, compare with solvent-borne type, a little less than the initial stage cohesive force of no-solvent type caking agent, except the problems such as easy generation bad order, also need custom-built machine, thereby be difficult to universal.In addition, known have to improve initial stage cohesive force and solidify after the physical property high solid caking agent that is object, solids component to 40% also can be coated with (for example, patent documentation 2 with reference to), but the application's problem is to seek further higher-solid.When higher-solid ground is coated with further, must make further the molecular weight of adhesive resin reduce, in this case, just the initial stage cementability after lamination significantly reduces, and has the problem such as shorten in work-ing life (usable time after solidifying agent coordinates) under generation tunnelling (floating when film is bonding), higher-solid.Therefore, present situation be the fluid,matching solids component more than 50% that not yet obtains caking agent, just the initial stage bonding strength bonding strength high and under normal conditions after lamination high, boil and distill the caking agent of patience excellence.
That is to say, it is that under initial stage bonding strength that 50 quality % also can be coated with when above, that tunnelling degree does not occur while having at lamination further, normality, bonding strength is high and boiling and the two-solution curing type lamination adhesive composite of the problems such as splitting is not occurring during the high-temperature sterilization treatment such as distillation that problem of the present invention is to provide nonvolatile component at adhesive composite, and the laminating method while using said composition.
Patent documentation 1: TOHKEMY 2003-129024
Patent documentation 2: TOHKEMY 2005-298588
Summary of the invention
The problem that invention will solve
It is that 50 quality % also can be coated with when above, lamination excellent that problem of the present invention is to provide nonvolatile component at adhesive composite, boil and the two-solution curing type lamination adhesive composite of the problems such as splitting does not occur during the high-temperature sterilization treatment such as distillation, and the laminating method while using said composition.
The means of dealing with problems
Found: the two-solution curing type lamination adhesive composite that the polyvalent alcohol polyhydroxy reactant of take is solidifying agent as host, the polymeric polyisocyanate composition of take, by being formed in the two-solution curing type lamination adhesive composite that uses specific polyester polyol composition in host with specified quantitative, can address the above problem, thereby complete the present invention.
That is to say, the invention provides two-solution curing type lamination adhesive composite, it is characterized in that: be to take polyester polyol composition as host, the two-solution curing type lamination adhesive composite that the polymeric polyisocyanate composition of take is solidifying agent, take and use the poly carboxylic acid or the polycarboxylic acid anhydride that contain the aromatic ring that derives from phthalic acid or Tetra hydro Phthalic anhydride (being OPA below) raw material more than every 1 gram of solids component 2.0 mmole (later unit is mmol/g) in the polyester polyol composition of host to obtain, and the polyester polyol composition of number-average molecular weight below 4000 is host.
Invention effect
According to the present invention, provide nonvolatile component at adhesive composite be that 50 quality % also can be coated with when above, there is not the initial stage bonding strength of tunnelling degree while having at lamination further and boil and the two-solution curing type lamination adhesive composite of the problems such as splitting do not occur during the high-temperature sterilization treatment such as distillation, and the laminating method while using said composition.
Working of an invention mode
Below to the detailed description of the invention.
Two-solution curing type lamination of the present invention is characterised in that with adhesive composite: be to take polyester polyol composition as the two-solution curing type lamination adhesive composite that host, the polymeric polyisocyanate composition of take are solidifying agent, take that to use that the poly carboxylic acid that contains the aromatic ring that derives from phthalic acid or Tetra hydro Phthalic anhydride (OPA) raw material more than every 1 gram of solids component 2.0 mmole (later unit is mmol/g) in the polyester polyol composition of host or polycarboxylic acid anhydride obtain and the polyester polyol composition of number-average molecular weight below 4000 be host.
Two-solution curing type lamination of the present invention is used in following dry lamination technical field with adhesive composite: in a side material face, by after caking agent coating, make solvent evaporation drying and remove, by other materials heating, crimping and stacked dry lamination technical field.
Two-solution curing type lamination of the present invention can make arbitrarily film freely laminating each other with adhesive composite, can obtain having the composite membrane of the performance of the object complied with, and is therefore widely used in the manufacture of the high performance packaging material for food of requirement.
Two-solution curing type lamination of the present invention requires (1) in order to prevent the unsteady initial stage cementability that is called as tunnelling after lamination just with adhesive composite, (2) for the high normality cementability of various plastic films, metal steam plated film and tinsel etc., (3) that boils, do not occur during the high-temperature sterilization treatment such as distillation splitting boils, distills the relevant high-performance such as patience, in order to there is these functions, as dry lamination caking agent, use the two-solution curing type urethane adhesive being formed by host and solidifying agent.
Host as two-solution curing type lamination of the present invention with adhesive composite, is used polyester polyol composition.
That is to say that the polyester polyol constitutive material as two-solution curing type lamination of the present invention by the host of adhesive composite is used phthalic acid or Tetra hydro Phthalic anhydride (OPA).
Phthalic acid refers to 1,2-phthalic acid
Tetra hydro Phthalic anhydride (OPA) refers to 1,2-phthalate anhydride
By the raw material using these phthalic acids or Tetra hydro Phthalic anhydride (OPA) as polyester, use, can not reduce initial stage cohesive force ground lowering viscousity.In addition, the work-ing life (usable time) after solidifying agent cooperation described later also can be than use m-phthalic acid (IPA), terephthalic acid (TPA) duration using in the past.
In addition, use the vibrin of Tetra hydro Phthalic anhydride (OPA), owing to being associated with lowering viscousity a little less than molecular interaction in solvent is when using IPA, TPA.
For the polyester polyol composition of host, preferably by use, contain that every 1 gram of solids component 2.0mmol/g is above, more preferably poly carboxylic acid or the polycarboxylic acid anhydride of the aromatic ring that derives from phthalic acid or Tetra hydro Phthalic anhydride (OPA) raw material of 2.5～4.5mmol/g obtain, and preferred number average molecular weight is below 4000.If used, contain every 1 gram of solids component 2.0mmol/g and derive from the poly carboxylic acid of aromatic ring of phthalic acid or Tetra hydro Phthalic anhydride (OPA) raw material or polycarboxylic acid anhydride and obtain, polyhydric alcohol solutions keeps the steady state of non-crystallizableization and suitable viscosity, and has guaranteed boiling patience and distilling patience of the compound film strength being formed by this adhesive composite laminating and the bag of being made by same film.If used, contain every 1 gram of solids component 2.5～4.5mmol/g and derive from the poly carboxylic acid of aromatic ring of phthalic acid or Tetra hydro Phthalic anhydride (OPA) raw material or polycarboxylic acid anhydride and obtain, just the normality bonding strength of initial stage shearing resistance, the lamination after lamination after aging further increases, the bag of being made by this adhesive composite boil patience and distillation patience also improves.
On the other hand, solidifying agent as two-solution curing type lamination of the present invention with adhesive composite, common material, the affixture that uses 3 moles of organic diisocyanate additions of addition in 1 mole of trimethylol propane and obtain, the biuret that 1 mole of water is reacted with 3 moles of organic diisocyanates and obtain, or the multifunctional organic multiple isocyanate with mode of connection such as isocyanuric acid esters being obtained by 3 moles of organic diisocyanate polymerizations, or use polyisocyanates and polyester polyol, react with low molecular polylol and the urethane polyisocyanate compound that obtains polyether glycol or as required they.
Further, the solids component after preferred aforementioned host coordinates with solidifying agent is more than 50%, examine grace cup viscosity under #3 in the scope of 13～30 seconds, more preferably in the scope of 13～20 seconds.
The vibrin using in the present invention is by making polyprotonic acid react and obtain with polyol, be that phthalic acid or Tetra hydro Phthalic anhydride (OPA) take that every 1 gram of solids component 2.0mmol/g contains above to make in its aromatic acid, number-average molecular weight below 4000 is the two-solution curing type lamination adhesive composite of feature, as other polyprotonic acid, so long as known, can use any raw material.
For example, can use succsinic acid separately or with the form of two or more mixtures, hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, maleic anhydride, fumaric acid, 1, 3-pentamethylene dicarboxylic acid, 1, 4-cyclohexane cyclohexanedimethanodibasic, terephthalic acid, m-phthalic acid, phthalic acid, 1, 4-naphthalene dicarboxylic acids, 2, 5-naphthalene dicarboxylic acids, 2, 6-naphthalene dicarboxylic acids, naphthalic acid, diphenyl dicarboxylic acid, 1, two (phenoxy group) ethane-p of 2-, the acid anhydrides of p '-dicarboxylic acid and these dicarboxylic acid or ester formative derivative, to Para Hydroxy Benzoic Acid, the ester formative derivative of p-(2-hydroxyl-oxethyl) M-nitro benzoic acid and these dihydroxy carboxylic acids, the polyprotonic acids such as dimeracid.
In addition, as polyol so long as known existence just can use arbitrarily.As concrete example, can be separately or make spent glycol with the form of two or more mixtures, propylene glycol, 1,3-PD, BDO, 1,5-PD, 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol, neopentyl glycol, methyl pentanediol, dimethylbutadio, butyl ethyl propylene glycol, glycol ether, triglycol, Tetraglycol 99, dipropylene glycol, tripropylene glycol, two hydroxyl-oxethyl benzene, Isosorbide-5-Nitrae-cyclohexanediol, Isosorbide-5-Nitrae-dimethanol hexanaphthene, triglycol, polycaprolactone glycol, dimer diol (Dimer diol), dihydroxyphenyl propane, the glycolss such as Hydrogenated Bisphenol A, propiolactone, butyrolactone, 6-caprolactone, δ-valerolactone, the polyester that the cyclic ester compounds such as Beta-methyl-δ-valerolactone obtain by ring-opening polymerization, by ethylene glycol, glycol ether, triglycol, propylene glycol, trimethylene glycol, 1,3 butylene glycol, BDO, 1,6-hexylene glycol, neopentyl glycol etc. have a kind of compound of 2 active hydrogen atoms or two or more as initiator by ordinary method by oxyethane, propylene oxide, butylene oxide ring, Styrene oxide 98min., epichlorohydrine, tetrahydrofuran (THF), 1 kind of the monomers such as tetrahydrobenzene or two or more addition polymerization and the polyol compositions such as polyethers that obtain.
In addition, two-solution curing type lamination of the present invention is with using adhesion promoters in caking agent.Adhesion promoters can be enumerated silane coupling agent, titanic acid ester is coupling agent, the epoxy resin etc. such as coupling agent, aluminium system.
As silane coupling agent, can enumerate aminosilanes such as γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane, N-β (amino-ethyl)-gamma-amino propyl trimethoxy silicane, N-β (amino-ethyl)-gamma-amino oxypropyl trimethyl dimethoxy silane, N-phenyl-gamma-amino propyl trimethoxy silicane; The epoxy silanes such as β-(3,4-epoxy cyclohexane) ethyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl triethoxyl silane; The vinyl silanes such as vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-methacryloxypropyl trimethoxy silane; Hexamethyldisilazane, γ mercaptopropyitrimethoxy silane etc.
As titanic acid ester, be coupling agent, can enumerate such as tetraisopropoxy titanium, four titanium n-butoxide, butyl (tetra) titanate dimer, four stearic acid titanic acid ester, titanium acetylacetone, lactic acid titanium, metatitanic acid four ethohexadiols, lactic acid titanium, four stearic oxygen base titaniums (テ ト ラ ス テ ア ロ キ シ チ タ Application) etc.
As epoxy resin, can enumerate the various epoxy resin such as general commercially available Epi-Bis type, phenolic varnish type, β methyl epoxy chloropropane (メ チ Le エ ピ Network ロ) type, ring-type ethylene oxide type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, multi-carboxylate's type, amino Racemic glycidol fundamental mode, Resorcinol type.
Further, lamination of the present invention, with in caking agent, as the acid proof method that improves bond layer, can also be used known acid anhydrides simultaneously.As acid anhydrides, can enumerate for example Tetra hydro Phthalic anhydride, succinyl oxide, hexachloro endoethylene tetrahydrophthalic acid acid anhydride (het anhydride), carbic anhydride (himic anhydride), maleic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, benzenetricarboxylic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 5-(2,5-oxo-tetrahydrofuran base)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride etc.
As operable diluting solvent, can enumerate ester classes such as vinyl acetic monomer, N-BUTYL ACETATE, cellosolve acetate, the ketones such as acetone, methyl ethyl ketone, isobutyl ketone, pimelinketone, the ethers such as tetrahydrofuran (THF), dioxan, toluene, dimethylbenzene etc. are aromatic hydrocarbon based, the halogenated hydrocarbons such as methylene dichloride, ethylene chloride, methyl-sulphoxide, methyl-sulphoxide acid amides etc.Wherein conventionally preferably use vinyl acetic monomer.
Caking agent of the present invention can be coated with by known any coating process, but generally by plate gravure coating method, is coated with.The glue spread of this caking agent is 1.5～5g/m at solids component
2, be preferably 2～4g/m
2coating condition under use.
Embodiment
By the following examples content of the present invention and effect are described in detail further, but the present invention is not subject to the restriction of following example.What in addition, in example, " part " represented is " weight part ".
The modulation of (modulation example 1) polyvalent alcohol A-1
(phthalic acid is the vibrin of OPA, aromatic series concentration 3.0mmol/g, molecular weight Mn=1500)
In possessing the pet reaction container of stirrer, thermometer, nitrogen ingress pipe, bead tube, wet separator etc., add 40.5 parts of Tetra hydro Phthalic anhydrides, 21.5 parts of sebacic acid, 11.4 parts of ethylene glycol, 26.6 parts of neopentyl glycol, the mode that is no more than 100 ℃ with bead tube upper temp heats lentamente and makes interior temperature remain on 240 ℃.Acid number becomes 2.0mgKOH/g when following, esterification is finished and obtain polyester polyol.It is 80% that the polyester polyol obtaining is made to nonvolatile component with vinyl acetic monomer dilution, using it as polyvalent alcohol A-1.
The modulation of (modulation example 2) polyvalent alcohol A-2
(phthalic acid is the vibrin of OPA, aromatic series concentration 3.5mmol/g, molecular weight Mn=1500)
In possessing the pet reaction container of stirrer, thermometer, nitrogen ingress pipe, bead tube, wet separator etc., add 47.8 parts of Tetra hydro Phthalic anhydrides, 13.4 parts of sebacic acid, 11.7 parts of ethylene glycol, 27.1 parts of neopentyl glycol, with bead tube upper temp, be no more than the mode of 100 ℃ and heat lentamente and make interior temperature remain on 240 ℃.Acid number becomes 2.0mgKOH/g when following, esterification is finished and obtain polyester polyol.It is 80% that the polyester polyol obtaining is made to nonvolatile component with vinyl acetic monomer dilution, using it as polyvalent alcohol A-2.
The modulation of (modulation example 3) polyvalent alcohol A-3
(phthalic acid is the vibrin of OPA, aromatic series concentration 2.5mmol/g, molecular weight Mn=1500)
In possessing the pet reaction container of stirrer, thermometer, nitrogen ingress pipe, bead tube, wet separator etc., add 33.6 parts of Tetra hydro Phthalic anhydrides, 29.1 parts of sebacic acid, 11.2 parts of ethylene glycol, 26.1 parts of neopentyl glycol, with bead tube upper temp, be no more than the mode of 100 ℃ and heat lentamente and make interior temperature remain on 240 ℃.Acid number becomes 2.0mgKOH/g when following, esterification is finished and obtain polyester polyol.It is 80% that the polyester polyol obtaining is made to nonvolatile component with vinyl acetic monomer dilution, using it as polyvalent alcohol A-3.
The modulation of (modulation example 4) polyvalent alcohol A-4
(phthalic acid is the vibrin of OPA, aromatic series concentration 2.0mmol/g, molecular weight Mn=4000)
In possessing the pet reaction container of stirrer, thermometer, nitrogen ingress pipe, bead tube, wet separator etc., add 26.6 parts of Tetra hydro Phthalic anhydrides, 39.2 parts of sebacic acid, 10.3 parts of ethylene glycol, 23.9 parts of neopentyl glycol, with bead tube upper temp, be no more than the mode of 100 ℃ and heat lentamente and make interior temperature remain on 240 ℃.Acid number becomes 2.0mgKOH/g when following, esterification is finished and obtain polyester polyol.It is 80% that the polyester polyol obtaining is made to nonvolatile component with vinyl acetic monomer dilution, using it as polyvalent alcohol A-4.
The modulation of (modulation example 5) polyvalent alcohol B
(phthalic acid is the vibrin of OPA, aromatic series concentration 1.8mmol/g, molecular weight Mn=1500)
In possessing the pet reaction container of stirrer, thermometer, nitrogen ingress pipe, bead tube, wet separator etc., add 24.0 parts of Tetra hydro Phthalic anhydrides, 39.9 parts of sebacic acid, 10.9 parts of ethylene glycol, 25.2 parts of neopentyl glycol, with bead tube upper temp, be no more than the mode of 100 ℃ and heat lentamente and make interior temperature remain on 240 ℃.Acid number becomes 2.0mgKOH/g when following, esterification is finished and obtain polyester polyol.It is 80% that the polyester polyol obtaining is made to nonvolatile component with vinyl acetic monomer dilution, using it as polyvalent alcohol B.
(modulation example 6) modulation polyvalent alcohol C
(phthalic acid is the vibrin of OPA, aromatic series concentration 2.5mmol/g, molecular weight Mn=5000)
In possessing the pet reaction container of stirrer, thermometer, nitrogen ingress pipe, bead tube, wet separator etc., add 33.4 parts of Tetra hydro Phthalic anhydrides, 32.5 parts of sebacic acid, 11.5 parts of ethylene glycol, 22.6 parts of neopentyl glycol, with bead tube upper temp, be no more than the mode of 100 ℃ and heat lentamente and make interior temperature remain on 240 ℃.Acid number becomes 2.0mgKOH/g when following, esterification is finished and obtain polyester polyol.It is 80% that the polyester polyol obtaining is made to nonvolatile component with vinyl acetic monomer dilution, using it as polyvalent alcohol C.
(modulation example 7) modulation polyvalent alcohol D
(phthalic acid is the vibrin of TPA, aromatic series concentration 3.0mmol/g, molecular weight Mn=1500)
In possessing the pet reaction container of stirrer, thermometer, nitrogen ingress pipe, bead tube, wet separator etc., add 43.9 parts of terephthalic acids, 19.8 parts of sebacic acid, 10.9 parts of ethylene glycol, 25.4 parts of neopentyl glycol, with bead tube upper temp, be no more than the mode of 100 ℃ and heat lentamente and make interior temperature remain on 240 ℃.Acid number becomes 2.0mgKOH/g when following, esterification is finished and obtain polyester polyol.It is 80% that the polyester polyol obtaining is made to nonvolatile component with vinyl acetic monomer dilution, using it as polyvalent alcohol D.
(modulation example 8) modulation polyol E
(phthalic acid is the vibrin of IPA, aromatic series concentration 3.0mmol/g, molecular weight Mn=1500)
In possessing the pet reaction container of stirrer, thermometer, nitrogen ingress pipe, bead tube, wet separator etc., add 43.9 parts of m-phthalic acids, 19.8 parts of sebacic acid, 10.9 parts of ethylene glycol, 25.4 parts of neopentyl glycol, with bead tube upper temp, be no more than the mode of 100 ℃ and heat lentamente and make interior temperature remain on 240 ℃.Acid number becomes 2.0mgKOH/g when following, esterification is finished and obtain polyester polyol.It is 80% that the polyester polyol obtaining is made to nonvolatile component with vinyl acetic monomer dilution, using it as polyol E.
(modulation example 9) modulation polyvalent alcohol F
(phthalic acid is the vibrin of TPA/IPA=45/55, aromatic series concentration 3.0mmol/g, molecular weight Mn=1500)
In possessing the pet reaction container of stirrer, thermometer, nitrogen ingress pipe, bead tube, wet separator etc., add 19.8 parts of terephthalic acids, 24.1 parts of m-phthalic acids, 19.8 parts of sebacic acid, 10.9 parts of ethylene glycol, 25.4 parts of neopentyl glycol, with bead tube upper temp, be no more than the mode of 100 ℃ and heat lentamente and make interior temperature remain on 240 ℃.Acid number becomes 2.0mgKOH/g when following, esterification is finished and obtain polyester polyol.It is 80% that the polyester polyol obtaining is made to nonvolatile component with vinyl acetic monomer dilution, using it as polyvalent alcohol F.
(modulation example 10) modulation polyvalent alcohol G
(phthalic acid is the vibrin of TPA/IPA=45/55, aromatic series concentration 2.5mmol/g, molecular weight Mn=1500)
In possessing the pet reaction container of stirrer, thermometer, nitrogen ingress pipe, bead tube, wet separator etc., add 16.3 parts of terephthalic acids, 19.9 parts of m-phthalic acids, 28.0 parts of sebacic acid, 10.8 parts of ethylene glycol, 25.0 parts of neopentyl glycol, with bead tube upper temp, be no more than the mode of 100 ℃ and heat lentamente and make interior temperature remain on 240 ℃.Acid number becomes 2.0mgKOH/g when following, esterification is finished and obtain polyester polyol.It is 80% that the polyester polyol obtaining is made to nonvolatile component with vinyl acetic monomer dilution, using it as polyvalent alcohol G.
(embodiment 1～3)
By by modulation each polyhydric alcohol solutions of obtaining of example 1～3 and solidifying agent Sumidur N-3210(Sumitomo Bayer urethane (Sumitomo バ イ エ Le Application) company system fat family polymeric polyisocyanate) in the mode of hydroxyl: isocyanate group=1.0:1.2, coordinate, further with vinyl acetic monomer, being diluted to solids component is 60%, obtains adhesive composite.By this adhesive composite use test laminating machine (Test Laminator) (the wild machine of Musashi (strain) system), take glue spread as 3.0g(nonvolatile component)/m
2at ONy(biaxial tension nylon) be coated with on film, in being the moisture eliminator of 70 ℃, Temperature Setting make diluting solvent volatilization be dried, to be coated with adhesive side and the LLDPE film lamination of the ONy of adhesive composite, make by 2 layers of composite membrane forming 1 of ONy/LLDPE, by 2 layers of composite membrane forming 2 of ONy/CPP.Then, this composite membrane is carried out to 40 ℃ * 3 days aging, carry out solidifying of adhesive composite and obtain the composite membrane of 2 layers.Film is used following material.
ONy film: You Niji can (strain) Emblem15 μ processed m
LLDPE film: Tohcello(strain) TUX-HC60 μ m processed
CPP film: eastern beautiful film processing (strain) ZK-93K70 μ processed m
(comparative example 1～6)
Each polyhydric alcohol solutions that replacement obtains by modulation example 1～4, the polyhydric alcohol solutions that use obtains by modulation example 5～10, in addition, with the adhesive composite that embodiment 1～4 similarly obtains, use this adhesive composite by obtaining the composite membrane of 2 layers with the same program of embodiment 1～4.
For the composite membranes of 2 layers that obtain, evaluate following items.
(1) goods stability (outward appearance)
Check the outward appearance of each polyhydric alcohol solutions after 25 ℃ * 1 month
Zero: good
*: gonorrhoea (visible crystallization)
(2) coordinate viscosity
For the adhesive composite of above-mentioned cooperation, at 25 ℃, with examining grace cup #3, measure number of seconds.
More than zero: 13 second～be less than 20 seconds
△: more than 20 seconds～be less than 30 seconds
*: more than 30 seconds
(3) viscosity after promotion
During the mensuration of the viscosity of the adhesive composite of above-mentioned cooperation after 40 ℃ * 6 hours, at 25 ℃, with examining grace cup #3, measure number of seconds.
More than zero: 13 second～be less than 30 seconds
*: more than 30 seconds
(4) initial stage shearing resistance is measured
For the material after the just lamination under following condition, at 25 ℃ of atmosphere temperatures, use tensile testing machine, peeling rate is set as to 5mm/ minute, by stretching test machine determination shearing resistance.
Zero: more than 1N/225mm2 left and right
*: be less than 1N/225mm2 left and right
(5) normality bonding strength
To at 25 ℃ of atmosphere temperatures, use tensile testing machine, peeling rate is set as 300mm/ minute, and the tensile strength while measuring the composite membrane 1 after aging with T-shaped stripping means is as bonding strength.
Zero: more than 7N/15mm
*: be less than 7N/15mm
(6) boil patience
Use composite membrane 1 after aging to make the bag of 120mm * 120mm size, as content, fill 70g coordinates vinegar, salad oil, meat sauce plan food with weight ratio 1:1:1.For the bag of making, by visual assessment, at 98 ℃, boil the outward appearance of the bag of germicidal treatment after 60 minutes.
Zero: outward appearance is unchanged
*: splitting
(7) distillation patience
Use composite membrane 2 after aging to make the bag of 120mm * 120mm size, as content, fill 70g coordinates vinegar, salad oil, meat sauce plan food with weight ratio 1:1:1.For the bag of making, by the outward appearance of visual assessment steam-type distillation germicidal treatment bag after 30 minutes at 121 ℃.
Zero: outward appearance is unchanged
*: splitting
Evaluation result is shown in table 1 and table 2.
Table 1
Table 2
Industry utilizability
High solid type adhesive composite of the present invention goes for field widely such as packaging material for food, electronic material mechanicals etc. that application forms the laminating such as plastic film, tinsel, paper composite membrane matrix material etc.
Claims (2)
1. a two-solution curing type lamination adhesive composite, it is characterized in that, it is for take the two-solution curing type lamination adhesive composite that polyester polyol composition is solidifying agent as host, the polymeric polyisocyanate composition of take, using and use that poly carboxylic acid or polycarboxylic acid anhydride obtain and the polyester polyol composition of number-average molecular weight below 4000 as host, described poly carboxylic acid or polycarboxylic acid anhydride contain with amounts more than every 1 gram of solids component 2.0 mmole in polyester polyol composition the aromatic ring that derives from phthalic acid or Tetra hydro Phthalic anhydride raw material.
2. two-solution curing type lamination adhesive composite according to claim 1, wherein, the solids component after host coordinates with solidifying agent is more than 50%, in the time of 25 ℃, examining grace cup viscosity is within the scope of 13～30 seconds in #3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-135146 | 2011-06-17 | ||
| JP2011135146 | 2011-06-17 | ||
| PCT/JP2012/065227 WO2012173182A1 (en) | 2011-06-17 | 2012-06-14 | High-solid adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103140559A CN103140559A (en) | 2013-06-05 |
| CN103140559B true CN103140559B (en) | 2014-02-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280003191.6A Active CN103140559B (en) | 2011-06-17 | 2012-06-14 | High-solid adhesive composition |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2671931B1 (en) |
| JP (1) | JP5167438B2 (en) |
| CN (1) | CN103140559B (en) |
| ES (1) | ES2730200T3 (en) |
| WO (1) | WO2012173182A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015178360A1 (en) * | 2014-05-20 | 2015-11-26 | Dic株式会社 | 2-component curable polyurethane laminate adhesive composition, laminate film, and food packaging material |
| CN106159127A (en) * | 2016-08-26 | 2016-11-23 | 上海紫江新材料科技有限公司 | Stainless steel foil and TPO composite lithium ion battery flexible packaging film and preparation thereof |
| JP6834702B2 (en) * | 2017-03-31 | 2021-02-24 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition |
| JP6642688B1 (en) * | 2018-11-30 | 2020-02-12 | 東洋インキＳｃホールディングス株式会社 | Laminating adhesive having release properties from composite film, laminate, and method for recycling sheet-like substrate |
| EP3888908B1 (en) * | 2018-11-30 | 2023-11-15 | Toyo Ink SC Holdings Co., Ltd. | Adhesive, packaging material, packaging container, and production method for recycled substrate |
| WO2024176385A1 (en) * | 2023-02-22 | 2024-08-29 | 東洋製罐株式会社 | Multilayer film using solventless adhesive, method for producing same, and packaging container |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003013032A (en) * | 2001-06-26 | 2003-01-15 | Dainippon Ink & Chem Inc | Adhesive composition for laminating having excellent retort resistance |
| JP2003129024A (en) * | 2001-10-25 | 2003-05-08 | Dainippon Ink & Chem Inc | Adhesive composition for laminate and the laminate |
| JP2007146162A (en) * | 2005-11-26 | 2007-06-14 | Bayer Materialscience Ag | Aqueous dispersion of urethane group-containing hydroxy functional polyester |
| JP2008045101A (en) * | 2006-07-18 | 2008-02-28 | Dainichiseika Color & Chem Mfg Co Ltd | Polyurethane resin and use thereof |
| JP2010023379A (en) * | 2008-07-22 | 2010-02-04 | Toyo Seikan Kaisha Ltd | Multilayer film using solventless adhesive, method for production thereof, and packaging container |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4530704B2 (en) | 2004-04-08 | 2010-08-25 | 東洋モートン株式会社 | High solid adhesive composition |
| US9676976B2 (en) * | 2010-06-21 | 2017-06-13 | Dic Corporation | Oxygen-barrier film and adhesive |
-
2012
- 2012-06-14 ES ES12801408T patent/ES2730200T3/en active Active
- 2012-06-14 CN CN201280003191.6A patent/CN103140559B/en active Active
- 2012-06-14 WO PCT/JP2012/065227 patent/WO2012173182A1/en active Application Filing
- 2012-06-14 EP EP12801408.1A patent/EP2671931B1/en active Active
- 2012-06-14 JP JP2012546284A patent/JP5167438B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003013032A (en) * | 2001-06-26 | 2003-01-15 | Dainippon Ink & Chem Inc | Adhesive composition for laminating having excellent retort resistance |
| JP2003129024A (en) * | 2001-10-25 | 2003-05-08 | Dainippon Ink & Chem Inc | Adhesive composition for laminate and the laminate |
| JP2007146162A (en) * | 2005-11-26 | 2007-06-14 | Bayer Materialscience Ag | Aqueous dispersion of urethane group-containing hydroxy functional polyester |
| JP2008045101A (en) * | 2006-07-18 | 2008-02-28 | Dainichiseika Color & Chem Mfg Co Ltd | Polyurethane resin and use thereof |
| JP2010023379A (en) * | 2008-07-22 | 2010-02-04 | Toyo Seikan Kaisha Ltd | Multilayer film using solventless adhesive, method for production thereof, and packaging container |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2671931A4 (en) | 2014-12-24 |
| ES2730200T3 (en) | 2019-11-08 |
| JP5167438B2 (en) | 2013-03-21 |
| JPWO2012173182A1 (en) | 2015-02-23 |
| EP2671931A1 (en) | 2013-12-11 |
| CN103140559A (en) | 2013-06-05 |
| WO2012173182A1 (en) | 2012-12-20 |
| EP2671931B1 (en) | 2019-03-20 |
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